AU2011214268B2 - Process for manufacturing succinic acid - Google Patents

Process for manufacturing succinic acid Download PDF

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AU2011214268B2
AU2011214268B2 AU2011214268A AU2011214268A AU2011214268B2 AU 2011214268 B2 AU2011214268 B2 AU 2011214268B2 AU 2011214268 A AU2011214268 A AU 2011214268A AU 2011214268 A AU2011214268 A AU 2011214268A AU 2011214268 B2 AU2011214268 B2 AU 2011214268B2
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monovalent
succinate
salt
succinic acid
solution
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Willem Jacob Groot
Jan Van Breugel
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Purac Biochem BV
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41Preparation of salts of carboxylic acids
    • C07C51/412Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/02Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42Separation; Purification; Stabilisation; Use of additives
    • C07C51/43Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02Dicarboxylic acids
    • C07C55/10Succinic acid
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/02Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/18Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic polyhydric
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/40Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/44Polycarboxylic acids
    • C12P7/46Dicarboxylic acids having four or less carbon atoms, e.g. fumaric acid, maleic acid

Abstract

The present invention discloses a Process for the preparation of succinic acid comprising the steps of : a) providing an aqueous medium comprising magnesium succinate by fermentation, wherein a carbohydrate source is fermented by means of a micro-organism to form succinic acid, a magnesium base being added as neutralising agent during fermentation to provide the magnesium succinate; b) subjecting the aqueous medium comprising magnesium succinate to a crystallisation step and a salt exchange step to provide an aqueous solution comprising a monovalent succinate salt, wherein the salt exchange, which is performed either prior to or after crystallisation, comprises treating the magnesium succinate with a monovalent base to provide a magnesium base and the monovalent succinate salt; c) adjusting the concentration of the monovalent succinate salt in the aqueous solution to a value between 10 and 35 wt.%; d) subjecting the aqueous solution comprising the monovalent succinate salt to water-splitting electrodialysis, to produce a first solution comprising monovalent base and a second solution comprising succinic acid and monovalent succinate salt, the electrodialysis being carried out to a partial conversion of 40 to 95 mole%; e) separating the second solution comprising succinic acid and monovalent succinate salt into succinic acid and a solution comprising the monovalent succinate salt by crystallisation; f) recycling the solution of step e) comprising the monovalent succinate salt to step d).

Description

WO 2011/098598 PCT/EP20111/052128 Process for manufacturing succinic acid 5 The present invention pertains to a process for manufacturing succinic acid in high purity in an economical manner. Succinic acid is often manufactured via fermentation of carbohy drates by micro-organisms. A common feature to all fermentation 10 processes is the need to neutralise the acids excreted by the micro-organisms. A drop in pH below a critical value, depending on the micro-organism used in the process, could damage the mi cro-organism's metabolic process and bring the fermentation process to a stop. Therefore, it is common practice to add a 15 base in the fermentation media in order to control the pH. This results in the succinic acid produced being present in the fer mentation media in the form of a succinate salt. Despite the longstanding practice to produce succinic acid via 20 fermentation, one of the challenges in the manufacture of suc cinic acid is still to obtain the acid in a relatively pure form while at the same time carrying out the process in an economical manner on a scale which is commercially attractive. 25 Electrodialysis is one of the purification processes that may be used in the production of succinic acid via fermentation. Water splitting electrodialysis in particular allows the direct con version of the succinate salt into succinic acid and base. In this type of electrodialysis bipolar membranes are generally 30 used to split water into H+ and OH respectively, which combine with the anion and cation of the succinate salt respectively, resulting in the production of separate solutions of succinic acid and base.

WO 2011/098598 PCT/EP2011/052128 2 EP 2 157 185 describes a process for the production of an ammo nium succinate solution which comprises crystallisation/fermentation steps for producing calcium succi nate trihydrate, a transfer step for transferring/crystallising 5 calcium succinate trihydrate to calcium succinate monohydrate, a crystal separation step, a salt-substitution step for converting the calcium succinate to an ammonium succinate solution and a solid/liquid separation step for removing calcium carbonate pre cipitate from the ammonium succinate solution. The document 10 indicates that the ammonium succinate is a suitable intermediate for the production of fermentation derived succinic acid by known methods, for instance a method using acetic acid. US 2007/0015264 describes the production of an organic acid am 15 monium solution, such as ammonium succinate, comprising the steps of obtaining a fermentation broth containing organic acid magnesium salt by using an organic acid producing microorganism in the presence of a magnesium compound, subjecting the organic acid magnesium salt contained in the fermentation broth to salt 20 exchange using an ammonia compound to produce organic acid ammo nium salt and magnesium compound, and separating the produced magnesium compound to obtain the organic acid ammonium salt so lution. The document mentions that the organic acid ammonium salt obtained may be used to obtain organic acid by several 25 methods including electrodialysis, ion-exchange resin, neutrali sation with sulfuric acid, reactive crystallisation and reactive extraction, without further details being given. US 5,034,105 describes a process for preparing a carboxylic 30 acid, (preferably succinic acid) which comprises the steps of preparing an undersaturated solution of a salt of the carboxylic acid (preferably a sodium succinate solution obtained after con centration of a sodium succinate-comprising fermentation broth by desalting electrodialysis), subjecting the solution to water 35 splitting electrodialysis to form base and a supersaturated so- WO 2011/098598 PCT/EP2011/052128 3 lution of the carboxylic acid and crystallising the carboxylic acid from the supersaturated solution. EP 0 389 103 describes a process for the production and purifi 5 cation of succinic acid which comprises the steps of producing a succinate salt through fermentation, subjecting the fermentation broth to a desalting electrodialysis process to recover the suc cinate salt as a concentrated succinate salt solution and subjecting the salt solution to water-splitting electrodialysis 10 to form a base and succinic acid. The succinic acid product is then treated with a strongly acidic ion exchanger in the acid form to remove any sodium or other cations followed by a weakly basic ion exchanger in the free base form to remove any sulfate ions or sulfuric acid and to obtain a highly purified succinic 15 acid product. The disadvantage of using ion exchangers is the need to regenerate the ion exchange resins, which generates waste by-products. This document does not suggest subjecting the succinate salt obtained via fermentation to a salt exchange re action. 20 There is still need for a process for manufacturing succinic acid which provides succinic acid in high purity and which can be performed in an economical manner with a low power consump tion, without producing substantial amounts of non-reusable 25 components (i.e. waste by-products) and without substantial yield loss. The present invention provides such a process, i.e. the process as defined by Claim 1. In this process magnesium succinate is 30 provided by fermentation and treated by means of crystallisation and salt exchange to provide an aqueous solution of a monovalent succinate salt which is especially suited for subsequent water splitting electrodialysis. Succinic acid of high purity is pro duced by using water-splitting electrodialysis with a partial 35 conversion of the succinate salt to succinic acid, separating WO 2011/098598 PCT/EP2011/052128 4 the succinic acid from the succinate salt by crystallization and recycling the succinate salt to the electrodialysis process. It has been found that the process for the manufacture of suc 5 cinic acid as described herein is very efficient and economical, provides high production yields, minimal product losses and re sults in succinic acid of high quality. Accordingly, the present invention pertains to a process for the 10 preparation of succinic acid comprising the steps of: a) providing an aqueous medium comprising magnesium succinate by fer mentation, wherein a carbohydrate source is fermented by means of a micro-organism to form succinic acid, a magnesium base being added as neutralising agent during fermentation to provide the magnesium suc 15 cinate; b) subjecting the aqueous medium comprising magnesium succinate to a crystallisation step and a salt exchange step to provide an aqueous solution comprising a monovalent succinate salt, wherein the salt ex change, which is performed either prior to or after crystallisation, 20 comprises treating the magnesium succinate with a monovalent base to provide a magnesium base and the monovalent succinate salt; c) adjusting the concentration of the monovalent succinate salt in the aqueous solution to a value between 10 and 35 wt.%; d) subjecting the aqueous solution comprising the monovalent succi 25 nate salt to water-splitting electrodialysis, to produce a first solution comprising monovalent base and a second solution comprising succinic acid and monovalent succinate salt, the electrodialysis be ing carried out to a partial conversion of 40 to 95 mole%; e) separating the second solution comprising succinic acid and mono 30 valent succinate salt into succinic acid and a solution comprising the monovalent succinate salt by crystallisation; f) recycling the solution of step e) comprising the monovalent succi nate salt to step d).

WO 2011/098598 PCT/EP2011/052128 5 The use of magnesium base during the fermentation step a) advan tageously results in the formation of magnesium succinate, which is soluble in the fermentation broth. The inventors have found that a separate and controlled crystallisation can be performed 5 from a fermentation broth neutralised with magnesium base. This is not the case when using other bases such as a calcium base. The use of calcium base generates calcium succinate, which tends to crystallise during fermentation in a less controlled manner than magnesium succinate. In addition, the calcium succinate 10 crystals obtained tend to be more difficult to separate from the fermentation broth. As a result of the crystallisation and salt exchange steps per formed on the magnesium succinate obtained via fermentation, the 15 aqueous solution comprising monovalent succinate salt provided in step b) is of such quality that it may be directly subjected to water-splitting electrodialysis to provide succinic acid. Carrying out the water-splitting electrodialysis to a partial 20 conversion of 40 to 95 mole% and subsequently recycling the re maining succinate salt to the electrodialysis step advantageously results in an optimal process with low power con sumption and no substantial yield loss. 25 Furthermore, the process as described herein produces virtually no waste by-products, since all compounds formed and separated in the different steps may be recycled. The magnesium base of step b) may for instance be used in the fermentation step a) and the solution comprising monovalent base of step d) may be used 30 in the salt exchange of step b). The separation step e) also contributes to minimise the amount of non-reusable components since it does not generate further waste by-products. The aqueous medium comprising magnesium succinate is provided by 35 a fermentation process. The magnesium succinate salt is gener- WO 2011/098598 PCT/EP2011/052128 6 ally already present in an aqueous medium when it leaves the fermentation. In such a process, a carbohydrate source is fer mented to succinic acid by means of a succinic acid-producing micro-organism. During fermentation, a magnesium base is added 5 as neutralising agent. This results in the formation of an aque ous medium comprising the corresponding magnesium succinate salt. The base anion of the magnesium base is preferably chosen from 10 at least one of hydroxide, carbonate and hydrogencarbonate, and more preferably is hydroxide. Although the use of magnesium as the base cation is preferred, another alkaline earth metal cation, such as a calcium cation, may also be used. The amount of alkaline earth metal base added is determined by the amount 15 of succinic acid produced and may be determined via pH control of the fermentation medium. The biomass (i.e. microbial cell matter) may be removed from the fermentation broth before further processing of the succinate 20 containing medium. Biomass removal may be effected, for example, by conventional methods including filtration, flotation, sedi mentation, centrifugation, flocculation and combinations thereof. It is within the skills of the skilled person to deter mine an appropriate method. Other optional treatments prior to 25 further processing include washing, filtration, (re)crystallisation, concentration and combinations thereof. The aqueous medium comprising the alkaline earth metal succinate salt, preferably magnesium succinate, is subjected to a crystallisa 30 tion step and a salt exchange step to provide an aqueous solution comprising a monovalent succinate salt. The monovalent succinate salt obtained is especially suitable for water-splitting electrodialysis since it is substantially free of fermentation-derived products (e.g. sugar, protein, amino acids) which may negatively interfere in water- WO 2011/098598 PCT/EP2011/052128 7 splitting electrodialysis by, for instance, increasing the power con sumption and fouling of the ion-permeable membranes. The salt exchange step, which may be performed either prior to 5 or after crystallisation, comprises treating the alkaline earth metal succinate salt with a monovalent base to provide an alka line earth metal base and the monovalent succinate salt. The monovalent base used in the salt exchange is preferably a 10 hydroxide, carbonate and/or hydrogencarbonate, more preferably a hydroxide, of a monovalent cation, the monovalent cation being sodium, potassium, lithium, ammonium, monoalkylammonium, dial kylammonium, trialkylammonium or tetraalkylammonium, preferably sodium or potassium and more preferably sodium. Generally, the 15 use of sodium and potassium bases advantageously results in a higher conversion of the alkaline metal earth succinate salt to the monovalent succinate salt than when ammonium bases are used. This is relevant for preparing a product with a low alkaline earth metal ion content suitable for water-splitting electrodi 20 alysis. The base anion is generally chosen to correspond to the base anion used as neutralising agent during fermentation. The amount of monovalent base is determined by stoichiometric and pH considerations. It may be preferred to use a surplus of 25 base to obtain a high conversion and to ensure the removal of virtually all alkaline earth metal ions from the succinate. The alkaline earth metal base obtained as a result of the salt exchange of step b) may be recycled to the fermentation step a). 30 The crystallisation may comprise at least one of a concentration step, such as a water evaporation step, a cooling step, a seed ing step, a separation step, a washing step and a re crystallisation step. Concentration may be performed as a sepa- WO 2011/098598 PCT/EP2011/052128 8 rate step or together with crystallisation (e.g. evaporative crystallisation). When crystallisation is performed prior to salt exchange, the 5 alkaline earth metal succinate salt is crystallised from the aqueous medium provided by fermentation by concentrating the fermentation broth (e.g. by evaporation of water), preferably after biomass removal. The alkaline earth metal succinate crys tals obtained are then separated from the liquid phase, which 10 contains the fermentation-derived products, providing a purified alkaline earth metal succinate salt. The salt exchange may then be performed in batch or in continuous mode. In batch mode, an aqueous solution comprising a monovalent base is slowly added to a solution or slurry containing the alkaline earth metal succi 15 nate salt. The alkaline earth metal base formed in the salt exchange step typically is in solid form while the monovalent succinate salt is dissolved in the aqueous phase. The salt ex change may preferably be performed in continuous mode. When the salt exchange is performed in continuous mode, a slurry of the 20 alkaline earth metal succinate salt crystals (e.g. magnesium succinate) and an aqueous solution of the monovalent base (e.g. sodium hydroxide) are mixed in a reactor to generate a slurry comprising the alkaline earth metal base in solid form (e.g. magnesium hydroxide) and the monovalent succinate salt dissolved 25 in the aqueous phase (e.g. sodium succinate). The two resulting components may be separated by conventional solid-liquid separa tion processes, such as filtration and/or sedimentation, providing the aqueous solution comprising the monovalent succi nate salt. 30 When the salt exchange is performed prior to crystallisation, the monovalent base is added to the aqueous medium comprising the alkaline earth metal succinate salt provided by fermenta tion, preferably after biomass removal. As discussed above, the 35 solid alkaline earth metal base formed may be separated from the WO 2011/098598 PCT/EP2011/052128 9 aqueous medium comprising the aqueous soluble monovalent succi nate salt. The monovalent succinate salt is then crystallised from the aqueous medium by concentrating the aqueous medium (e.g. by evaporation of water) and the crystals are separated 5 from the liquid phase, which contains the fermentation-derived products, providing a purified monovalent succinate salt. The aqueous solution comprising the monovalent succinate salt may be obtained by for example dissolving the separated succinate crys tals in water. 10 The aqueous solution of monovalent succinate salt may be sub jected to additional treatments prior to water-splitting electrodialysis, such as ion exchange treatment, activated car bon treatment, desalting electrodialysis, dilution, 15 concentration and/or filtration (e.g. nanofiltration). For in stance, as a safety measure to prevent a too high alkaline earth metal level in the aqueous solution comprising the monovalent succinate salt, an ion exchange step may be performed prior to electrodialysis to lower the alkaline earth metal content 20 thereof. However, the process as described herein advantageously does not necessitate such additional treatments, especially when a magne sium base is added in the fermentation process to provide a 25 magnesium succinate fermentation broth. The aqueous solution comprising the monovalent succinate salt is then subjected to water-splitting electrodialysis. 30 The initial concentration of the monovalent succinate salt in the aqueous solution that is subjected to electrodialysis (the feed solution) is between 10 and 35 wt.%. Preferably, the mono valent succinate salt concentration is between 20 and 35 wt.%, more preferably between 20 and 30 wt.% and most preferably be 35 tween 22 and 28 wt.%. Depending on the salt concentration, the WO 2011/098598 PCT/EP2011/052128 10 aqueous solution comprising the monovalent succinate salt may be used directly after step b), or, if necessary, may be diluted or concentrated to adjust the salt concentration prior to water splitting electrodialysis. Concentration may be carried out by 5 for instance evaporation or desalting electrodialysis. The concentration of the monovalent succinate salt in the aque ous medium may be determined by methods known to the skilled person, for instance by using conductivity measurements or In 10 ductively Coupled Plasma mass spectrometry analysis. The water-splitting electrodialysis is carried out to a partial conversion of 40 to 95 mole%. Preferably, the electrodialysis is carried out to a conversion of 50 to 95 mole%, more preferably 15 of 60 to 95 mole%, even more preferably of 70 to 90 mole%, even more preferably of 80 to 90 mole%, and most preferably of 85 mole%. A first solution comprising monovalent base and a second solution comprising succinic acid and monovalent succinate salt are produced in this process. 20 A partial conversion of 40 to 95 mole% means that 40 to 95 mole% of the monovalent succinate salt is converted into succinic acid. This results in the second solution produced by the elec trodialysis comprising succinic acid in an amount of 40 to 95 25 mole%, calculated on the total molar amount of succinic acid and succinate present in the solution. The degree of conversion may be monitored by measuring conduc tivity of the second solution using methods known to the person 30 skilled in the art. In addition to the conversion level and the initial salt concen tration of the feed solution, the conductivity of the second solution will depend on the temperature of the electrodialysis 35 process. The higher the temperature at which the electrodialysis WO 2011/098598 PCT/EP2011/052128 11 is performed, the lower the power consumption will be. Hence, the working temperature is chosen to optimise power consumption without compromising the performance and the life of the ion specific permeable membranes. Generally, the water-splitting 5 electrodialysis is performed at a temperature between 25 *C and 40 0C. However, it is preferred to conduct the electrodialysis at a temperature higher than 50 0C, for instance between 60 *C and 80 *C, to allow for a low power consumption and the possi bility for heat recovery. 10 Because of the limited solubility of succinic acid in water, in order to avoid crystallisation of succinic acid during water splitting electrodialysis, the working conditions of the elec trodialysis are chosen to ensure that the concentration of 15 succinic acid in the final solution is below saturation. For in stance, for a conversion of 40 to 95 mole% and a working temperature of 25 'C, at which the solubility of succinic acid in water is about 8 wt.%, the initial sodium succinate concen tration should be between 10 and 25 wt.%. When working at higher 20 temperatures, the concentration of sodium succinate in the feed solution may be higher. The water-splitting electrodialysis as described herein may be performed using a conventional apparatus and conventional meth 25 ods. Preferably the water-splitting electrodialysis is carried out in an electrodialysis apparatus provided with a cation ex change membrane and a bipolar membrane. A typical water splitting electrodialysis cell comprises a series of a two com partment unit, generally a series of about 50 units. The aqueous 30 medium comprising the monovalent succinate salt is introduced in the salt/acid compartment (or feed compartment). The monovalent cations are transported from the salt/acid compartment to the base compartment through the cation exchange membrane to produce the first solution comprising the monovalent base. Simultane 35 ously, H+ ions are transported to the salt/acid compartment to WO 2011/098598 PCT/EP2011/052128 12 produce the second solution comprising succinic acid and monova lent succinate salt. It is preferred to apply the water-splitting electrodialysis to 5 monovalent succinate salts of sodium and potassium. When using ammonium succinate, care must be taken to control the emission of toxic ammonia resulting from the generation of ammonium hy droxide. 10 The second solution produced by the water-splitting electrodi alysis is separated into succinic acid and a solution comprising the monovalent succinate salt by crystallisation. The succinic acid may be crystallised in a static crystallisa 15 tion unit, by fractional crystallisation, by suspension crystallisation and/or by wash column crystallisation. The crys tallisation may comprise a concentration step, such as a water evaporation step, a cooling step and/or a seeding step and one or more washing steps. The crystals may then be separated from 20 the liquid phase of the solution crystals by filtration or cen trifugation. The solution containing the monovalent succinate salt obtained after separation step e), which may comprise residual succinic 25 acid, is recycled to the water-splitting electrodialysis. This recycling step ensures that no substantial yield loss is suf fered as a consequence of the partial conversion of the succinate into succinic acid during water-splitting electrodi alysis. 30 The succinic acid obtained after the separation step e) is gen erally in solid form (e.g. crystalline) and has a purity of at least 99 wt.%, preferably at least 99.5 wt.%, more preferably at least 99.7 wt.% and most preferably at least 99.9 wt.%. 35 WO 2011/098598 PCT/EP2011/052128 13 The succinic acid obtained by the process according to the in vention is of high purity and is suitable for direct use in numerous applications such as synthetic processes, food applica tions and cosmetic applications. The succinic acid can be 5 directly used as a monomer in polymerisation processes (e.g. for the formation of polyamides) or as a precursor of other impor tant products and synthetic intermediates such as succinic acid esters, succinic acid anhydride and diamino butane. The succinic acid obtained is particularly suited for the production of buta 10 ncdiol (c.g. by hydrogenation), which is an important intermediary product in polymer production. The process as described herein advantageously is accompanied by a low power consumption and ensures that no or substantially no 15 waste by-products are generated. The present invention is further illustrated by the following Examples, without being limited thereto or thereby. 20 Example 1: Crystallisation of magnesium succinate. In a jacketed 0.5 L vessel 150.0 g of magnesium succinate tetra hydrate (synthesised from succinic acid 99% from Acros and magnesium oxide 98% from Acros) was suspended in 199.9 g of de 25 mineralised water, in order to obtain a magnesium succinate content of 28 wt.% (expressed as anhydrate). To this mixture 8.1 g of sodium lactate (60%, Purasal S from Purac), as well as 2.6 g of sodium acetate (anhydrous from Fluka) and 10.0 g of yeast extract paste (65% from Bio Springer) were added to simulate a 30 succinic acid fermentation broth and to track the presence of impurities in the final magnesium succinate crystals. The mixture was heated by means of a thermostatic bath to 90 *C, in order to dissolve all solids. After 30 minutes the solution 35 still contained solids. Each 30 minutes some water was added to a total amount of 147.4 g. At this stage all de solids were dis solved and the total volume was about 450 ml.

WO 2011/098598 PCT/EP2011/052128 14 The mixture was cooled from 90 to 20 *C in 5 hours and allowed to stir during the night. No solids were formed. The mixture was heated again to 80 *C and 100 ml of water was allowed to evapo 5 rate. Then the concentrated solution was cooled from 80 *C to 60 0 C in 30 minutes and seed crystals were added. Then the mixture was cooled linearly from 60 *C to 20 *C in 3 hours. During the cool 10 ing crystallization nucleation took place at 37 *C The resulting suspension was separated by means of a filtering centrifuge. After centrifugation an amount of 72.8 g of solid magnesium succinate was obtained. 15 The samples were analysed on sodium content, lactate and acetate content, total nitrogen content and colour (APHA, a known method for the measurement of colour). The results are shown in Table 1. 20 Table 1 acetic lactic total fresh Na sample acid acid nitrogen colour (wt.%) (wt.%) (mg/kg) (mg/kg) (APHA) 1 crystals 0.22 0.23 820 390 121 2 Mother liquor 0.69 0.68 6400 3100 n.a. This is the colour of a 10% solution in water at 50 *C. 25 The amount of impurities in the magnesium succinate crystals is significantly reduced compared to the amount of impurities in the mother liquor. In addition, the colour-value measured in the solution of the magnesium succinate crystals indicates that the 30 residual colour in the crystals is very low.

WO 2011/098598 PCT/EP2011/052128 15 The purity of the magnesium succinate crystals may be improved by washing of the crystals. Example 2: Salt exchange of calcium succinate and magnesium suc 5 cinate with monovalent base. Preparation of starting materials: For preparation of magnesium succinate in an aqueous medium (solu 10 tion), 80.0 g of succinic acid were dissolved in 1000.0 g of water. After heating to 50 0C, a stoichiometric amount of solid magnesium oxide (27.3 g) was added. To make sure all of the succinic acid would react, a small surplus (2.3 g) of MgO was added. Finally, the mixture was filtered over a Buchner funnel, equipped with a filter paper. The 15 filtrate, being a 9.4 wt.% solution of magnesium succinate, was col lected. Calcium succinate in an aqueous medium (suspension) was prepared in an analogous manner by letting succinic acid (80.0 g + 4.2 g surplus in 1000.1 g water) react with solid calcium hydroxide (50.6 g). After filtration and washing with approximately 800 ml of 20 demineralised water, the residue (calcium succinate) was collected and dried in a desiccation stove for 18 hours at 80 0C. The calcium succinate was then suspended in water. The slight surplus of reagents in both reactions was applied in order to obtain succinates with a minimal amount of impurities. 25 Experiments: Magnesium succinate and calcium succinate were reacted with various bases to investigate the effectivity of the salt exchange process. 30 The following monovalent bases were used: sodium hydroxide [NaOH], sodium carbonate [Na 2 CO3], ammonium carbonate [(NH 4 )2CO 3 ] and ammonium hydroxide [NH 4 0H]. The reactions were carried out in 500 ml beakers or Erlenmeyer flasks 35 containing 100 ml of 10 wt.% magnesium succinate or calcium succinate WO 2011/098598 PCT/EP2011/052128 16 in aqueous medium. Sodium carbonate and ammonium carbonate were added in solid form in stoichiometric amounts. Ammonia and NaOH were added in solute form, also in stoichiometric amounts. The reaction mixtures were stirred using a stirring bar and a magnetic stirrer. The amounts 5 of alkaline earth metal succinate and monovalent base used in each reaction are shown in Table 2. Table 2 Exp. # Reaction m(Mg/Ca-Succ.) Base [g] [g] 1 MgSucc + NH 4 0H 99.7 9.2 2 MgSucc + NaOH 100.0 10.8 (+ 89.4 H20) 3 MgSucc + Na 2

CO

3 99.9 7.2 4 MgSucc + (NH 4

)

2

CO

3 99.6 6.5 5 CaSucc + NH40H 10.0 + 89.8 H 2 0 8.8 6 CaSucc + NaOH 10.0 + 90.1 H20 10.5 7 CaSucc + Na 2

CO

3 10.0 + 90.1 H20 6.8 8 CaSucc + (NH 4

)

2

CO

3 10.0 + 90.1 H20 6.1 10 The mixtures were allowed to react for 1 hour. From each reaction mixture, samples of 25 ml were taken. These were centrifuged, after which Mg (or Ca) and succinate were determined analytically. The ana lytical data and the initial concentration of Mg 2 /Ca 2 or succinate 15 were used for calculation of the conversion of magnesium succinate or calcium succinate to sodium or ammonium succinate. The results are given in Table 3.

WO 2011/098598 PCT/EP2011/052128 17 Table 3 Experiment pH Mg/Ca Succinate Conversion [ppm] [wt.%] [%] 1: MgSucc + NH 4 0H 9.6 8415 6.9 43.0 2: MgSucc + NaOH 12.4 12 4.0 99.8 3: MgSucc + Na 2

CO

3 10.5 880 7.7 94.1 4: MgSucc + (NH 4

)

2

CO

3 7.8 9487 7.5 37.4 5: CaSucc + NH 4 0H 11.1 3489 1.0 12.7 6: CaSucc + NaOH 13.0 281 6.5 95.4 7: CaSucc + Na 2

CO

3 10.5 19 7.0 99.3 8: CaSucc + (NH 4

)

2

CO

3 8.0 829 7.0 98.7 As can be seen from Table 3, when sodium hydroxide is used, a conver sion of well above 90% is obtained both for magnesium succinate and 5 for calcium succinate. The same applies when sodium carbonate is used. For ammonium carbonate it should be noted that while for cal cium succinate a conversion of 98.7% is obtained, the conversion for magnesium succinate is only 37.4%. 10 Example 3: Partial electrodialysis of a sodium succinate solu tion. An Electrocell electrodialysis module (Sweden) was equipped with a Fumatech FBM bipolar membrane, and a Neosepta CMB cation exchange 15 membrane. A set-up with two electrode compartment and one feed com partment was used. The membrane areas of the bipolar and the cation exchange membrane was 0.01 M 2 . The first compartment comprised of the anode and the cation exchange side of the bipolar membrane, the sec ond feed compartment of the anion exchange side of the bipolar 20 membrane and the cation exchange membrane, and the third compartment of the cation exchange membrane and the cathode. 2 wt.% sulfuric acid in water was circulated through the anode compartment to ensure a high conductivity. A 30.5 wt.% sodium succinate solution was circu lated through the middle compartment as a feed. The feed solution was 25 prepared by dissolving 237.6 g sodium succinate in 540.8 g demineral- WO 2011/098598 PCT/EP2011/052128 18 ised water. A 6 wt.% sodium hydroxide solution was circulated through the cathode compartment to ensure a high conductivity at the cathode side, and to collect the sodium hydroxide produced. The three solu tions were circulated with a peristaltic pump at 250 ml/min from a 5 500 ml glass buffer over the electrodialysis module. The glass buffer vessels were double walled. The sulphuric acid, sodium hydroxide were reagent grade, and the Purac sodium succinate was of high purity food grade quality. 10 The temperature across the thrc compartments was kept between 40 and 60 'C with a water bath. The electrodialysis experiment was carried out a constant 7.5 A DC current. No crystallisation of succinic acid was observed in the electrodyalisis module during the experiment. 15 During water-splitting electrodialysis the sodium succinate solution in the feed compartment of the module is acidified batch wise through sodium removal through the cation exchange membrane to form sodium hydroxide in the cathode compartment, while protons generated by the bipolar membrane form succinic acid with the original succinate ions. 20 In the beginning of the experiment the conductivity of the feed (so dium succinate solution) was about 160 mS/cm and the voltage about 10 V. During the first 250 minutes of the experiment the voltage in creased slowly to 11 V, coinciding with a conductivity decrease. In 25 the interval between 550 and 626 minutes the voltage had increased from about 12 V to 16 V and the conductivity decreased from about 50 mS/cm to 14.62 mS/cm. At this point the conversion was 95% and the experiment was stopped. 30 Voltage increase results in a rapid increase in power consumption to convert the residual sodium succinate. The solution comprising 36.7 wt.% of succinic acid and 2.8 wt.% of sodium succinate was cooled down to room temperature, during which 19 succinic acid crystals formed. The fluid was then poured off and the solid succinic acid was dried in a stove for 15 hours. Example 4: Crystallisation of succinic acid from a succinic ac 5 id/sodium succinate solution. In a crystalliser (500 ml open jacketed glass vessel) 100.1 g (0.848 mole) of succinic acid (Acros) and 19.9 g (0.074 mole) of sodium succinate hexahydrate (Acros) were dissolved in 281.5 g of 0 demineralised water, by heating with the thermostatic bath to 80 'C. This resulted in a clear solution with 25 % of succinic acid and 3 % of sodium succinate, representing a solution obtained from a water-splitting electrodialysis process with a conversion of 92 mole%. The solution was cooled from 80 'C to 20 'C in 5 hours with 5 a linear cooling profile. During cooling nucleation took place be tween 56 0 C and 50 0 C. The resulting crystals were separated by means of a filtering cen trifuge. After centrifugation an amount of 70.2 g of solid succinic 0 acid was obtained. Samples of the motherliquor and the succinic acid crystals were an alysed on sodium content, while the motherliquor was also analysed on succinate content. The crystals were analysed without drying. 25 The sodium content of the crystals was found to be 165 ppm, as com pared to 10400 ppm in the mother liquor, whereas the content of succinic acid in the mother liquor was of 12 wt.%. 30 The amount of sodium was considerably reduced in the crystals when compared to the motherliquor. The amount of sodium in the crystals may be lowered further by washing during centrifugation. In the claims which follow and in the preceding description of the 35 invention, except where the context requires otherwise due to ex 7429483 1 (GHMatters) P90995.AU GLENYSL 20 press language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclu sive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in 5 various embodiments of the invention. It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an ad mission that the publication forms a part of the common 0 general knowledge in the art, in Australia or any other coun try. 7429483 1 (GHMatters) P90995.AU GLENYSL

Claims (20)

1. A process for the preparation of succinic acid comprising the steps of: 5 a) providing an aqueous medium comprising magnesium succinate by fermentation, wherein a carbohydrate source is fermented by means of a micro-organism to form succinic acid, a magnesium base being added as neutralising agent during fermentation to provide the magnesium succinate; 0 b) subjecting the aqueous medium comprising magnesium succin ate to a crystallisation step and a salt exchange step to provide an aqueous solution comprising a monovalent succinate salt, wherein the salt exchange, which is performed either prior to or after crystallisation, comprises treating the magnesium succinate with a 5 monovalent base to provide a magnesium base and the monovalent suc cinate salt; c) adjusting the concentration of the monovalent succinate salt in the aqueous solution to a value between 10 and 35 wt.%; d) subjecting the aqueous solution comprising the monovalent 0 succinate salt to water-splitting electrodialysis, to produce a first solution comprising monovalent base and a second solution comprising succinic acid and monovalent succinate salt, the elec trodialysis being carried out to a partial conversion of 40 to 95 mole%; 5 e) separating the second solution comprising succinic acid and monovalent succinate salt into succinic acid and a solution com prising the monovalent succinate salt by crystallisation; f) recycling the solution of step e) comprising the monovalent succinate salt to step d). 30
2. The process according to claim 1, wherein in step b) the salt exchange is performed after crystallisation.
3. The process according to claim 1 or claim 2, wherein in 5 step c) the concentration of the monovalent succinate salt in 7429483 1 (GHMatters) P90995.AU GLENYSL 22 the aqueous solution is adjusted to a value between 20 and 35 wt.
4. The process according to claim 3, wherein in step c) the 5 concentration of the monovalent succinate salt in the aqueous solution is adjusted to a value between 20 and 30 wt.%.
5. The process according to any one of the preceding claims, wherein the electrodialysis step d) is carried out to a par 0 tial conversion of 50 to 95 mole%.
6. The process according to claim 5, wherein the electrodi alysis step d) is carried out to a partial conversion of 70 to 90 mole%. 5
7. The process according to claim 5, wherein the electrodi alysis step d) is carried out to a partial conversion of 80 to 90 mole%. 0
8. The process according to claim 3 or claim 4, wherein the electrodialysis is carried out to a partial conversion of 85 mole%.
9. The process according to any one of the preceding claims, 25 wherein the first solution comprising the monovalent base pro duced by the water-splitting electrodialysis step d) is recycled to step b).
10. The process according to any one of the preceding claims, 30 wherein the water-splitting electrodialysis is carried out in an electrodialysis apparatus provided with a cation exchange membrane and a bipolar membrane.
11. The process according to any one of the preceding claims, 35 wherein the magnesium base of step a) is magnesium hydroxide. 7429483 1 (GHMatters) P90995.AU GLENYSL 23
12. The process according to any one of the preceding claims, wherein the aqueous medium comprising the magnesium succinate is subjected to a separation step to remove microbial cell 5 matter prior to step b).
13. The process according to any one of the preceding claims, wherein the monovalent base in step b) comprises a cation that is a sodium, potassium, lithium, ammonium, monoalkylammonium, 0 dialkylammonium, trialkylammonium or tetraalkylammonium cati on.
14. The process according to claim 13, wherein the monovalent base in step b) comprises a sodium or potassium cation. 5
15. The process according to any one of the preceding claims, wherein the succinic acid obtained after the separation step e) is in solid form and has a purity of at least 99 wt.%. 0
16. The process according to claim 15, wherein the succinic acid obtained after the separation step e) is in solid form and has a purity of at least 99.5 wt.%.
17. The process according to claim 15, wherein the succinic 25 acid obtained after the separation step e) is in solid form and has a purity of at least 99.9 wt.%.
18. A process for the preparation of butanediol, comprising preparing succinic acid using the process according to any one 30 of the preceding claims and hydrogenating the succinic acid to form butanediol.
19. Succinic acid prepared by the process defined in any one of claims 1 to 17. 35 7429483 1 (GHMatters) P90995.AU GLENYSL 24
20. Butanediol prepared by the process defined in claim 18. 7429483 1 (GHMatters) P90995.AU GLENYSL
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